The influence of bridging ligand electronic structure on the photophysical properties of noble metal diimine and triimine light harvesting systems

Xian Yong Wang; Andre Del Guerzo; Sujoy Baitalik; Gerald Simon; George B. Shaw; Lin X. Chen; Russell Schmehl

doi:10.1007/s11120-005-9007-y

The influence of bridging ligand electronic structure on the photophysical properties of noble metal diimine and triimine light harvesting systems

Xian Yong Wang, Andre Del Guerzo, Sujoy Baitalik, Gerald Simon, George B. Shaw, Lin X. Chen, Russell Schmehl^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Review article › peer-review

52 Scopus citations

Abstract

This manuscript discusses the photophysical behavior of transition metal complexes of Ru(II) and Os(II) employed in development of light harvesting arrays of chromophores. Particular emphasis is placed on the relationship between the photophysical behavior of complexes having metal-to-ligand charge transfer (MLCT) excited states and the electronic characteristics of bridging ligands used in preparing oligometallic complexes. Examples are presented that discuss intramolecular energy migration in complexes having two distinct MLCT chromophores with bridging ligands that only very weakly couple the two chromophores. In addition, systems having bridging ligands with localized triplet excited states lower in energy than the MLCT state of the metal center to which they are attached are discussed. These systems very often have excited states localized on the bridging ligand with excited state lifetimes on the order of tens of microseconds. Finally, systems having Fe(II) metal centers, with very low energy MLCT states, are discussed. In complexes also containing bridging ligands with low energy triplet states, energy partitioning between the Fe center MLCT state (or Fe localized ligand field states) and the ligand triplet state is observed; the two states relax to the ground state via parallel pathways, but the Fe(II) center does not serve as an absolute excitation energy sink.

Original language	English (US)
Pages (from-to)	83-103
Number of pages	21
Journal	Photosynthesis Research
Volume	87
Issue number	1
DOIs	https://doi.org/10.1007/s11120-005-9007-y
State	Published - Jan 2006

Funding

The authors wish to thank the U.S. Department of Energy, Division of Science (#DE-FG02–96 ER14617) for support of this work. In addition, RHS wishes to thank the many graduate and undergraduate students that contributed a great deal to this work; some of their efforts are recognized in the citations in this article.

Keywords

Intraligand
Intramolecular energy transfer
Ligand localized
Metal-to-ligand charge transfer

ASJC Scopus subject areas

Biochemistry
Plant Science
Cell Biology

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10.1007/s11120-005-9007-y

Cite this

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title = "The influence of bridging ligand electronic structure on the photophysical properties of noble metal diimine and triimine light harvesting systems",

abstract = "This manuscript discusses the photophysical behavior of transition metal complexes of Ru(II) and Os(II) employed in development of light harvesting arrays of chromophores. Particular emphasis is placed on the relationship between the photophysical behavior of complexes having metal-to-ligand charge transfer (MLCT) excited states and the electronic characteristics of bridging ligands used in preparing oligometallic complexes. Examples are presented that discuss intramolecular energy migration in complexes having two distinct MLCT chromophores with bridging ligands that only very weakly couple the two chromophores. In addition, systems having bridging ligands with localized triplet excited states lower in energy than the MLCT state of the metal center to which they are attached are discussed. These systems very often have excited states localized on the bridging ligand with excited state lifetimes on the order of tens of microseconds. Finally, systems having Fe(II) metal centers, with very low energy MLCT states, are discussed. In complexes also containing bridging ligands with low energy triplet states, energy partitioning between the Fe center MLCT state (or Fe localized ligand field states) and the ligand triplet state is observed; the two states relax to the ground state via parallel pathways, but the Fe(II) center does not serve as an absolute excitation energy sink.",

keywords = "Intraligand, Intramolecular energy transfer, Ligand localized, Metal-to-ligand charge transfer",

author = "Wang, {Xian Yong} and {Del Guerzo}, Andre and Sujoy Baitalik and Gerald Simon and Shaw, {George B.} and Chen, {Lin X.} and Russell Schmehl",

note = "Funding Information: The authors wish to thank the U.S. Department of Energy, Division of Science (#DE-FG02–96 ER14617) for support of this work. In addition, RHS wishes to thank the many graduate and undergraduate students that contributed a great deal to this work; some of their efforts are recognized in the citations in this article.",

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doi = "10.1007/s11120-005-9007-y",

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T1 - The influence of bridging ligand electronic structure on the photophysical properties of noble metal diimine and triimine light harvesting systems

AU - Wang, Xian Yong

AU - Del Guerzo, Andre

AU - Baitalik, Sujoy

AU - Simon, Gerald

AU - Shaw, George B.

AU - Chen, Lin X.

AU - Schmehl, Russell

N1 - Funding Information: The authors wish to thank the U.S. Department of Energy, Division of Science (#DE-FG02–96 ER14617) for support of this work. In addition, RHS wishes to thank the many graduate and undergraduate students that contributed a great deal to this work; some of their efforts are recognized in the citations in this article.

PY - 2006/1

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N2 - This manuscript discusses the photophysical behavior of transition metal complexes of Ru(II) and Os(II) employed in development of light harvesting arrays of chromophores. Particular emphasis is placed on the relationship between the photophysical behavior of complexes having metal-to-ligand charge transfer (MLCT) excited states and the electronic characteristics of bridging ligands used in preparing oligometallic complexes. Examples are presented that discuss intramolecular energy migration in complexes having two distinct MLCT chromophores with bridging ligands that only very weakly couple the two chromophores. In addition, systems having bridging ligands with localized triplet excited states lower in energy than the MLCT state of the metal center to which they are attached are discussed. These systems very often have excited states localized on the bridging ligand with excited state lifetimes on the order of tens of microseconds. Finally, systems having Fe(II) metal centers, with very low energy MLCT states, are discussed. In complexes also containing bridging ligands with low energy triplet states, energy partitioning between the Fe center MLCT state (or Fe localized ligand field states) and the ligand triplet state is observed; the two states relax to the ground state via parallel pathways, but the Fe(II) center does not serve as an absolute excitation energy sink.

AB - This manuscript discusses the photophysical behavior of transition metal complexes of Ru(II) and Os(II) employed in development of light harvesting arrays of chromophores. Particular emphasis is placed on the relationship between the photophysical behavior of complexes having metal-to-ligand charge transfer (MLCT) excited states and the electronic characteristics of bridging ligands used in preparing oligometallic complexes. Examples are presented that discuss intramolecular energy migration in complexes having two distinct MLCT chromophores with bridging ligands that only very weakly couple the two chromophores. In addition, systems having bridging ligands with localized triplet excited states lower in energy than the MLCT state of the metal center to which they are attached are discussed. These systems very often have excited states localized on the bridging ligand with excited state lifetimes on the order of tens of microseconds. Finally, systems having Fe(II) metal centers, with very low energy MLCT states, are discussed. In complexes also containing bridging ligands with low energy triplet states, energy partitioning between the Fe center MLCT state (or Fe localized ligand field states) and the ligand triplet state is observed; the two states relax to the ground state via parallel pathways, but the Fe(II) center does not serve as an absolute excitation energy sink.

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The influence of bridging ligand electronic structure on the photophysical properties of noble metal diimine and triimine light harvesting systems

Abstract

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Keywords

ASJC Scopus subject areas

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